CN1163498C - Prepn. method for high-purity bisalkyl phosphate - Google Patents
Prepn. method for high-purity bisalkyl phosphate Download PDFInfo
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- CN1163498C CN1163498C CNB001195387A CN00119538A CN1163498C CN 1163498 C CN1163498 C CN 1163498C CN B001195387 A CNB001195387 A CN B001195387A CN 00119538 A CN00119538 A CN 00119538A CN 1163498 C CN1163498 C CN 1163498C
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- reaction
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- compound
- organic solvents
- pcl
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- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 20
- 239000010452 phosphate Substances 0.000 title claims abstract description 20
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims description 18
- 238000000034 method Methods 0.000 title description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 3
- 239000002904 solvent Substances 0.000 claims description 15
- 239000000047 product Substances 0.000 claims description 13
- 239000007795 chemical reaction product Substances 0.000 claims description 8
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 150000005826 halohydrocarbons Chemical class 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 238000007670 refining Methods 0.000 claims description 2
- 238000000605 extraction Methods 0.000 abstract description 6
- 238000001953 recrystallisation Methods 0.000 abstract description 5
- 125000000217 alkyl group Chemical group 0.000 abstract description 2
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 abstract 3
- -1 phosphate ester Chemical class 0.000 abstract 2
- 230000020477 pH reduction Effects 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 238000001816 cooling Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- QZRMKGRPCTVXBS-UHFFFAOYSA-N 2,6,8-trimethylnonan-4-yl dihydrogen phosphate Chemical compound CC(C)CC(C)CC(CC(C)C)OP(O)(O)=O QZRMKGRPCTVXBS-UHFFFAOYSA-N 0.000 description 3
- 150000003014 phosphoric acid esters Chemical class 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- UHGIMQLJWRAPLT-UHFFFAOYSA-N octadecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCCCCCCCOP(O)(O)=O UHGIMQLJWRAPLT-UHFFFAOYSA-N 0.000 description 2
- WRKCIHRWQZQBOL-UHFFFAOYSA-N octyl dihydrogen phosphate Chemical compound CCCCCCCCOP(O)(O)=O WRKCIHRWQZQBOL-UHFFFAOYSA-N 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- XINQFOMFQFGGCQ-UHFFFAOYSA-L (2-dodecoxy-2-oxoethyl)-[6-[(2-dodecoxy-2-oxoethyl)-dimethylazaniumyl]hexyl]-dimethylazanium;dichloride Chemical compound [Cl-].[Cl-].CCCCCCCCCCCCOC(=O)C[N+](C)(C)CCCCCC[N+](C)(C)CC(=O)OCCCCCCCCCCCC XINQFOMFQFGGCQ-UHFFFAOYSA-L 0.000 description 1
- 150000000211 1-dodecanols Chemical class 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Abstract
The present invention relates to a preparation method for C2 to C18 bisalkyl phosphate ester. Compounds of RO-X and PCl3 are used as raw materials, wherein R is a C2 to C18 alkyl group, and X is H, K, Na or Mg. Materials I are prepared from the compound of the RO-X and inert organic solvents, materials II are prepared from the compound of the PCl3 and the inert organic solvents, the materials I and the materials II react according to a charging ratio of the PCl3 to the RO-X = 1: (2 to 8), and the reaction temperature is 20 to 50 DEG C. After the reaction is finished, HCl gas in a system is removed, and the high-purity bisalkyl phosphate ester is directly prepared by neutralization, acidification, extraction, filtration, recrystallization, etc.
Description
The present invention relates to the preparation of bisalkyl phosphate, the carbonatoms that particularly relates to alkyl is the preparation of 2～18 bisalkyl phosphate.
Bisalkyl phosphate is widely used in many fields as a kind of fine chemical product, and can make smooth agent and static inhibitor behind the alkali reaction, and at domain of inorganic chemistry, bisalkyl phosphate is again a kind of metal extraction agent of excellent property.In field of fine chemical, bisalkyl phosphate can be used as the manufacturing raw material of some makeup.In addition, it also can be used as the intermediate of many lubricants and medicament.Usually, bisalkyl phosphate all is to pass through P
2O
5Having carried out esterification with corresponding Fatty Alcohol(C12-C14 and C12-C18) makes.As the preparation method of the disclosed a kind of static inhibitor of Chinese patent application CN 1080650A, wherein mentioned by dodecanol and P
2O
5And the potassium hydroxide reaction makes two 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite.But, the bisalkyl phosphate (salt) that the common method of this usefulness obtains usually and monoalkyl phosphoric acid esters mix, and because bisalkyl phosphate and single alkyl phosphonic acid ester structure are closely similar, physics, chemical property are very approaching, so be difficult to carry out separation and purification, and aggravate along with the growth of carbochain.Therefore, can't directly obtain highly purified bisalkyl phosphate with common preparation method.
The preparation method who the purpose of this invention is to provide a kind of bisalkyl phosphate by the improvement of technological process, can directly obtain highly purified bisalkyl phosphate, has overcome the defective that prior art exists effectively.
Preparation C provided by the invention
2～C
18The method of bisalkyl phosphate is with compound R O-X and PCl
3Be raw material, wherein R is C
2～C
18Alkyl, X is H, K or Na, may further comprise the steps:
1) compound R O-X and inert organic solvents are mixed with material I, and the mol ratio of RO-X and solvent is 1: (2～8), Compound P Cl
3Be mixed with material II, PCl with inert organic solvents
3With the mol ratio of solvent be 1: (2～8), material I and material II react, temperature of reaction is 20～50 ℃, feed ratio is PCl
3: RO-X=1: (2～8),
2) remove the HCl gas that reaction produces in the system after reaction finishes, add the solvent chloromethane in the product, the add-on by volume of solvent chloromethane be solvent for use total amount in the step 1) (0.7～1.3) doubly,
3) add alkali in the reaction product to being alkalescence, under 30～80 ℃, carry out neutralization reaction,
4) reaction product is acidified to and is acid, and layering extract oil phase materials, material are cooled to 10～40 ℃, and filtration obtains the crystallisate of separating out in the material, and the crystallisate recrystallizing and refining gets product.
The reaction equation of above-mentioned reaction process is:
Above-mentioned steps 1) inert organic solvents described in can adopt C usually
2～C
8Aliphatic hydrocarbon, halohydrocarbon or aromatic hydrocarbons.
When compound R O-X described in the step 1) and inert organic solvents were mixed with material I, the mol ratio of RO-X and solvent was preferably 1: (3～5); Compound P Cl
3When being mixed with material II with inert organic solvents, PCl
3Be preferably 1 with the mol ratio of solvent: (4～6), the reaction feed ratio is preferably PCl
3: RO-X=1: (2～5).
Compared with prior art, only the invention has the advantages that by selecting suitable solvent and the prepared in reaction process is made improvements slightly, but just direct reaction makes the higher bisalkyl phosphate of purity.
Come by the following examples that the invention will be further described.
Embodiment 1:
In three-necked flask, add 38 gram (0.45 mole) potassium ethylates, 200 milliliters of (1.4 moles) heptane, slowly drip down by 15 gram (0.11 mole) PCl in 20～25 ℃
3Mixed solution with 70 milliliters of (0.5 mole) heptane are mixed with reacted 5 hours down at 20～30 ℃.Take out the HCl gas that reaction produces in the system after reaction finishes, add 250 milliliters CCl again
4, drip 40% NaOH solution then, be alkalescence until reaction product.Reactant is heated to 70 ℃ refluxed 6 hours, product is acidified to HCl and is acid.Use the Petroleum ether extraction oil-phase product, bis ethane base phosphoric acid ester crystallisate is separated out behind the cooling sherwood oil, and filtration obtains crystallisate, and continues with sherwood oil recrystallization 2 times, at last white crystalline bis ethane base phosphoric acid ester, purity is 99%.
Embodiment 2:
In reactor, add 45 gram (0.35 mole) octanols, 200 milliliters of (1.4 moles) heptane, slowly drip down by 15 gram (0.11 mole) PCl in 25～32 ℃
3Mixed solution with 70 milliliters of (0.5 mole) heptane are mixed with reacted 5 hours down at 20～30 ℃.Take out the HCl gas that reaction produces in the system after reaction finishes, add 270 milliliters CHCl again
3, drip 30% KOH solution then, be alkalescence until reaction product.Reactant is heated to 80 ℃ refluxed product H 5 hours
2SO
4Be acidified to and be acid.Use the ether extraction oil-phase product, two octyl phosphoric acid ester crystallisates are separated out behind the cooling ether, and filtration obtains crystallisate, and continue with ether recrystallization 2 times, at last white crystalline pair octyl phosphoric acid ester, purity is 97%.
Embodiment 3:
In reactor, add 56 gram (0.3 mole) lauryl alcohols, 75 milliliters of (0.97 mole) ethylene dichloride, slowly drip down by 15 gram (0.11 mole) PCl in 45～50 ℃
3Mixed solution with 35 milliliters of (0.45 mole) ethylene dichloride are mixed with reacted 5 hours down at 40～50 ℃.Take out the HCl gas that reaction produces in the system after reaction finishes, add 110 milliliters CHCl again
3, drip 33% NaOH solution then, be alkalescence until reaction product.Reactant is heated to 50 ℃ refluxed product H 7 hours
2SO
4Be acidified to and be acid.Use the ether extraction oil-phase product, two 1-isobutyl-3,5-dimethylhexylphosphoric acid crystallisates are separated out behind the cooling ether, and filtration obtains crystallisate, and continue with ether recrystallization 2 times, at last white crystalline pair 1-isobutyl-3,5-dimethylhexylphosphoric acids, purity is 99%.
Embodiment 4:
In reactor, add 100 gram (0.37 mole) stearyl alcohol, 130 milliliters of (1.48 moles) benzene, slowly drip down by 15 gram (0.11 mole) PCl in 45～50 ℃
3Mixed solution with 45 milliliters of (0.5 mole) benzene are mixed with reacted 5 hours down at 40～50 ℃.Take out the HCl gas that reaction produces in the system after reaction finishes, add 170 milliliters CCl again
4, drip 20% NaOH solution then, be alkalescence until reaction product.Reactant is heated to 70 ℃ refluxed 5 hours, product is acidified to HCl and is acid.Use the ether extraction oil-phase product, two octadecyl phosphoric acid ester crystallisates are separated out behind the cooling ether, and filtration obtains crystallisate, and continue with ether recrystallization 2 times, at last white crystalline pair octadecyl phosphoric acid ester, purity is 97%.
Claims (3)
1, a kind of C
2～C
18The preparation method of bisalkyl phosphate is with compound R O-X and PCl
3Be raw material, wherein R is C
2～C
18Alkyl, X is H, K or Na, may further comprise the steps:
1) compound R O-X and inert organic solvents are mixed with material I, and the mol ratio of RO-X and solvent is 1: (2～8), Compound P Cl
3Be mixed with material II, PCl with inert organic solvents
3With the mol ratio of solvent be 1: (2～8), material I and material II react, temperature of reaction is 20～50 ℃, feed ratio is PCl
3: RO-X=1: (2～8),
2) remove the HCl gas that reaction produces in the system after reaction finishes, add the solvent chloromethane in the product, the add-on by volume of solvent chloromethane be solvent for use total amount in the step 1) (0.7～1.3) doubly,
3) add alkali in the reaction product to being alkalescence, under 30～80 ℃, carry out neutralization reaction,
4) reaction product is acidified to and is acid, and layering extract oil phase materials, material are cooled to 10～40 ℃, and filtration obtains the crystallisate of separating out in the material, and the crystallisate recrystallizing and refining gets product.
2, C according to claim 1
2～C
18The preparation method of bisalkyl phosphate is characterized in that the inert organic solvents described in the step 1) is C
2～C
8Aliphatic hydrocarbon, halohydrocarbon or aromatic hydrocarbons.
3, C according to claim 1
2～C
18The preparation method of bisalkyl phosphate, when it is characterized in that compound R O-X described in the step 1) and inert organic solvents are mixed with material I, the mol ratio of RO-X and solvent is 1: (3～5), Compound P Cl
3When being mixed with material II with inert organic solvents, PCl
3With the mol ratio of solvent be 1: (4～6), the reaction feed ratio is PCl
3: RO-X=1: (2～5).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001195387A CN1163498C (en) | 2000-08-01 | 2000-08-01 | Prepn. method for high-purity bisalkyl phosphate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001195387A CN1163498C (en) | 2000-08-01 | 2000-08-01 | Prepn. method for high-purity bisalkyl phosphate |
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| Publication Number | Publication Date |
|---|---|
| CN1336376A CN1336376A (en) | 2002-02-20 |
| CN1163498C true CN1163498C (en) | 2004-08-25 |
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|---|---|---|---|
| CNB001195387A Expired - Fee Related CN1163498C (en) | 2000-08-01 | 2000-08-01 | Prepn. method for high-purity bisalkyl phosphate |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2479180A1 (en) * | 2011-01-17 | 2012-07-25 | LANXESS Deutschland GmbH | Process for the preparation of alkylphosphates |
| CN104233793A (en) * | 2013-09-18 | 2014-12-24 | 上海天坛助剂有限公司 | Alkyl phosphate antistatic agent |
-
2000
- 2000-08-01 CN CNB001195387A patent/CN1163498C/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| CN1336376A (en) | 2002-02-20 |
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Granted publication date: 20040825 Termination date: 20100801 |